Process and apparatus for the thermal cracking of hydrocarbons



Fern, W, 14.

PROCESS AND APPARATUS FOR THE THERMAL CRACKING 0F HYDROCARBONS S. C. EASTWOOD ET AL Filed April 4, 1946 3 Sheets$heet l SYLVANDER C. EASTWOOD ROBERT D. DREW INVENTORS ATTORNEY Feb, 17, 1948- s. c. EASTWOOD ETAL PROCESS AND APPARATUS FOR THE IHERMAL CRACKING OF HYDROCARBONS Filed April 4, i946 3 Sheets-Sheet 2 SYLVANDER c. EASTWOOD ROBERT D. DREW INVENTORS BY I ATTORNEY e 17, 1948- s. c. EASTWOOD ETAL. 32

PROCESS AND APPARATUS FOR THE THERMAL CRACKING QF HYDROCARBONS Filed April 4, 1946 s Sheets-Sheet s FIG. 3 Y 62 PRODUCT on. 6 T 4m WATER SYLVANDER C. EASTWOOD ROBERT D. DREW INVENTORS ATTORNEY and thereafter rapidly quenching the reaction The granular Solids r re tor N e t urrso STATES FPATENT OFFICE PROCESS AND APPARATUS FOR TH'ETHER- MAL CRACKING OF HYDROCARBONS Sylvander 0. Eastwood, Woodbury, and Robert D. Drew, Wenonah, N. J., assignors to Sccony- Vacuum Oil Company, Incorporated, a corporation of New York Application April 4, 1946, Serial No. 659,448 3 Claims. (01. 196-55) This invention relates to apparatus for con- I Figure 3 is a vertical section through the'contact between a fluid and a solid and to a process. tactor in the reaction cycle. of contacting a fluid and a solid. More particu- Referring specifically to Figure 1, the embodilarly, the invention contemplates as a specific ment shown utilizes two separate circulating sysembodiment, apparatus and process for gener- 5; terms for granular solid. In the reaction cycle, ating and preheating a reaction mixture and for th solid is heated in a heater It and passed elevating the reaction mixture to a desired redownwardly at high temperature through a feed action temperature. le ll having a steam sealing zone l2 to a re- The invention is particularly well suited to a actor i3. In the reactor I3 hydrocarbon reactprocess for manufacture oi. ethylene and the like 1 ants are passed in direct contact with the hot by contacting a. hydrocarbon fraction such as a solid in a manner to be described in detail hereas oil or a topped crude in the presence of steam inafter. Spent solidsv from the reactor it pass with a hot granular solid to thereby raise the through a purging pot it to an elevator it. The temperature oi the reaction mixture to the depurging pot may advantageously be an enlarged sired reaction temperature (say 1400" to 1600 F.) zone held under slight vacuum by an injector i6.

mixture to halt the reaction. ferred in elevator to, for example at about 900 According to this invention, a compact bed of F., to a feed chute I? having a classifier IQ for hi ly heated granular solid is passed downwardv removal of small particles.

1y through a reactor through zones of decreasing In the quenching cycle, reaction mixture from temperature. In the uppermost zone a reaction reactor i 3 enters a quench chamber la'wherein mixture of hydrocarbon vapor and water vapor it is contacted with relatively cold granular solids is contacted with highly heated solids to thereby to reduce the temperature to a level below that produce the desired reaction temperature whereat which reaction occurs. This results in heating upon the reaction mixture is promptly quenched the granular solid and depositing thereon a comand the desired products recovered therefrom. bustible contaminant. The hot contaminated In B, dd e Z0 8 ydrocarbons are p e eated; solid passes by a feed leg 28 having a steamsealpreferably vaporized from the liquid state and me; zone 2| to a cooler 22 wherein the granular preheated, during concurrent how with respect solid is contacted with air or other suitable coolto the moving bed of solids. In a still lower zone, ing medium; the cold solid passing by line 23 to steam is superheated. preferably generated from elevator 24 from the top of which it enters chute liquid water and superheated. The hot oil vapors 25 having a classifier 28 and passes to a feed from the middle zone and the superheated steam hop er 21. The cold solids from feed hopper from the lowest zone are collected together, mixed 21 pass downwardly by ieedleg 28 equipped wi h and transferred to the uppermost zone as the rea steam sealing zone 29 to enter the quencher l9.

action mixture mentioned above. In the reaction specifically discussed herein as The objects and advantages of the invention exemplary, it is desirable to have a quantity of will be more clearly understood from considerateam mixed with the hydrocarbons during retion of a specific embodiment wherein the presaction. According to one embodiment of the inent inventlonis utilized aspart of acomplete sys- 4 ventlon. oil vapors are generated by injecting tem for the manufacture of ethylene from gas oil liquid oil from pump 80 directly into the bed of or the like. As an example. there will be considhot solids in reactor l8 and injecting liquid waered a process wherein the hot products of comter from pumpill to a lower point in the reactor bustion are quenched by contact with a relatively for. generation of steam. The oil and water cold granular solid, which solid is thereafter vapors are mixed within reactor l3 and transcooled by contact with air thus generating preferred by lines 32 to a higher point in the reactor heated air for use in burners to heat a separate wherein the mixed vapors contact granular solid cycle of granular solids employed for producing at its higher temperature and undergo reaction. the desired reaction temperature according to The reaction products are promptly transferred the invention. Such an exemplary embodiment by line- 33 to quench chamber l9 wherein their is shown in the annexed drawings; wherein temperature drops below that at which reaction Figural is a diagrammatic showing of atypical will take place and the cooled vapors pass by lin plant for practicing the invention; 34 toa, spray condenser 85 wherein a spray of Figure 2 is a vertical section through one type cold liquid from spray head it lowers the temof heater for the reaction cycle; and perature to such an extent that light hydrocaraccuse hon gases are separated from heavier hydrocarbons and pass overhead by line 81 to suitable fractionation and purification equipment. The liquid mixture of oil and water in the bottom of spra condenser 35 is transferred to a settler I. wherein water and oil are separated. the latter being transferred by line 19 through cooler 4| to storage or means for separation of valuable constituents thereof. The water layer from the bottom of settler 38 is removed by line 4i through cooler 42 and may be recycled in part to the spray head 36. A portion of the water from the bottom of settler :8 may be used for the generation of steam in reactor is since the system of steam.

generation used therein is fully capable of utilizing dirty water for generation of clean steam. Any contaminants in the water are deposited on the solid for later removal in the heater to by burning.

As noted above, air is passed through the cooling zone 22 wherein it is preheated and later used for generation of hot products of combustion' for heating of the granular solid in heater ll. Air for this purpose is supplied by compressor 43 and is heated in cooler 22 from which it is passed by line 44 to burners in heater ll. As shown, fuel, for example hydrocarbon gases, may

be supplied to the heater I! by compressor 45.

when utilizing a liquid fuel such as a heavy petroleum fraction, atomizing steam for the burners can be supplied to'the heater ID by line 48.

A typical structure for the heater II is shown in Figure 2 wherein the burners and gas-solid contact means are arranged around a central flue including the chimney 41 and a louvered .wall ll. the purpose or which will be brought out below. Granular solids are admitted to the heater by a feed pipe 49 from which they pass downward through an annular-space between the chimney 41 and a side wall It. In this annular space indirect heat exchange between hot gases and the incoming solid takes place to. aid in heating the granular solid. The preheated-solid then meets a dividing cone which splits the solid stream to an inner portion lying against the diverging bottom of chimney 41 and an outer portion which is exposed at its surface to a combustion chamber enclosed by a refractory arch 52.

Disposed below the arch I! are a plurality of ports 53 to receive burners for generation of a flame impinging directly upon the granular solids lying against the conical divider II. The hot products of combustion are transferred by a passage indicated generally at '54 to an annular space between the outer wall I of the heater and a second louvered wall it which defines a passage for the granular solids between the walls 4| and 56. The hot products of combustion pass transversely through I the downwardly moving solids to enter the central flue below chimney 41 from which they'are removed by the said chimney 41 to economizers orthelike. To insure even flow of the granularsolids between walls 48 and 56, there is provided a plate 51 across the bottom of the granular solid passage pierced by two rings of tubes and 5!. The tubes II in the outer ring are staggered'with respect to the tubes 58 in the inner ring thus providing a pinrality of withdrawal points spaced a short distance apart to minimize the small heap of nonflowing or slowly moving solids therebetween. Hot solids pass from pipes 58 and 59 downward to the feed leg it from. which they are transferred to the reactor is as previously noted.

A slightly different modification of the heater II is indicated in Figure 1 wherein the central line is defined by louvered walls below the burner as in Figure 2 and is also defined by similar louvered walls above the burner as indicated at 80. In this case the hot products of combustion from the lower heat transfer region pass to an upper heat transfer region above the burners, flow outwardly through solids between louvered walls and are removed by a port 6 l The reactor is of relatively simple structure but accomplishes the several functions of vaporizing oil and water. mixing the vapors and contacting the vapor mixture with highly heated solids. Solids admitted from feed leg li fall onto a tube sheet 02 from which a number of feed pipes 68 depend. The solids move downwardly as a compact bed below the feed pipes 63 past a plurality of vapor distributors O4 to a second tubesheet 85 which again has feed pipes 88 depending therefrom. The granular solids again move down as a compact bed past distributors i1. vapor collectors a and-distributors I! to a plate 10 having a plurality of withdrawal tubes 1| similar in function to tubes '8 and '59 shown in Fi ure 2. Plate 12 has a lesser number of openings than does plate I! to equalize withdrawal from the several pipes 1i and plate 18 has a still lesser number of openings for the same reason.

As the hot solids move downward through the reactor it they are gradually cooled but sufficient heat is retained to adequately vaporize the oil charge and the water admitted for generation of steam. The single vessel thus generates oil vapors from liquid admitted by line 30 and distributors 61 and generates steam from liquid water admitted by line 3! and distributor 69. The oil vapors move downwardly, since the pipes 66 constitute a seal of reasonable efiiciency, and mingle with steam at collector to to form a mixture of hydrocarbon vapors and water vapor which is transferred by line 32 and distributors 84 to the upper part of the chamber. This reaction mixture passes upwardly countercurrent to the very hot solids in the top of the reactor and is thus rapidly heated to the desired reaction temperature and passes into the space among tubes 03 which is free of solids, from which it is withdrawn by pipe 88 and transferred as described to quenching chamber to be rapidly cooled to a temperature below that at which reaction occurs.

A high yield of ethylene is produced at a mean effective temperature of 1454 F. and 0.40 second reaction time using 61.3% of steam by weight based on total charge. The granular solid used was particles of fused alumina at a maximum temperature during contact of about 1560 F. A granular solid to oil ratio of. 11.9 (based on weight) was employed at a space velocity of- 2.03

liquid volumes of gas oil' at F. per volume of' reaction space" per hour, calculating reaction space as that portion of the reactor wherein the charge is iinally'heated to reaction temperature and excluding vaporizingand preheating zones.

This operationlljmduce's 21.7% byweight of ethylene together with substantial amounts ofother oleflns including butadiene. butene', propylenes. etc. The process also yields of highly aromatic gasoline.

We claim:

1. A process for the thermal cracking of hydrocarbons which comprises passing a hot gran ular solid downwardly through acontacting zoneincluding a charge preparation section and a high temperature cracking section thereabove,

introducing liquid hydrocarbons to the upper part of said charge preparation section to be vaporized and preheated by contact with hot solids withdrawing said mixture from said charge preparation section and passing said mixture in direct contact with and countercurrent to the downwardly moving hot granular solid in said high temperature cracking section.

2. Apparatus for the thermal conversion of hydrocarbons comprising a vertical contacting chamber, means to admit granular solids to the top of said chamber, means to withdraw granularsolids from the bottom of said chamber, vertical pipes of restricted cross-section intermediate the ends of said chamber, a horizontal partition extending across said chamber at the level of the upper ends of said vertical pipes and pierced by said pipes to divert granular solids moving downward through said chamber to said vertical pipes to provide a sealing zone extending from said horizontal partition to the bottom of saidvertical pipes, fluid collecting means intermediate said sealing zone and the bottom of said chamber, a first fluid charge distributor intermediate said fluid collector and said sealing zone, a second fluid charge distributor intermediate said fluid collector and the bottom 01' said chamber, a third fluid charge distributor within said chamber above said sealing zone. means to withdraw fluid product from a point in the upper part of said chamber spaced above said third fluid charge distributor and means to transfer fluid from said fluid collecting means to said third fluid charge distributor.

3. A process for the thermal cracking of hydrocarbons which comprises passing a hot granular solid through a high temperature cracking zone, contacting a charge mixture of hydrocarbon vapors and steam with said solid in said cracking zone to thereby crack said vapors, thus lowering the temperature of said solid, passing granular solid so cooled from said cracking zone to a charge preparation zone, introducing hydrocarbons to said charge preparation zone and contacting said hydrocarbons with said solid in said charge preparation zone to heat the hydrocar bons by heat retained in the solid at the time of leaving said cracking zone. introducing water to said charge preparation zone and contacting said water therein with said solid to thereby vaporize and heat said water by means of heat retained in said solid, combining thejheated vapors of water and hydrocarbons to form a vaporous charge mixture and passing said mixture to said cracking zone as aforesaid.

SYLVANDER C. EASTWOOD. ROBERT D. DREW.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number 

